Insecticidal phenylhydrazine derivatives

ABSTRACT

Compounds having the structural formula     &lt;IMAGE&gt;  (I)    &lt;IMAGE&gt;  (II)  where X, Y, R and Z are defined in the specification are disclosed. The compounds of this invention are effective for controlling mites, nematodes, rice planthopper, tobacco budworm, and southern corn rootworm. Methods for making these compounds are also set forth.

CROSS REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 07/979,095, filed Nov. 10,1992, now U.S. Pat. No. 5,367,093, which is a continuation-in-part ofapplication Ser. No. 07/796,506, filed Nov. 22, 1991, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention is directed to novel phenylhydrazine derivatives whichexhibit activity as insecticides, acaricides and nematicides. Thisinvention is also directed to insecticidal, acaricidal or nematicidalcompositions comprising such compounds as well as to methods ofcontrolling insects, acarids and nematodes employing such compounds orcompositions.

Destruction by insects, acarids and nematodes presents a serious problemto agriculture. A wide variety of field crops are in need of protectionfrom nematodes, acarids, and insects including such valuable crops assoybeans, corn, peanuts, cotton, alfalfa, rice and tobacco. In addition,vegetables, such as tomatoes, potatoes, sugarbeet, carrots, peas, andthe like as well as fruits, nuts, ornamentals and seed bed crops such asapples, peaches, almonds, citrus fruit and grapes may also requireprotection from the ravages of such pests.

Consequently, the development of new, more effective pesticidesincluding insecticides, acaricides and nematicides represents an ongoingscientific activity. More particularly, the development of pesticideswhich are effective as both ovicides and larvicides are of interest.

2. Description of Related Art

Chemical Abstracts 108(19):163280d refers to alkylphenylhydrazinecarboxylates said to be useful as acaricides. U.S. Pat.No. 4,725,302 refers to substituted phenylhydrazines andphenyloxadiazolinones said to be useful as pesticides. European Patent 0067 471 refers to 7-substituted 2,3-dihydrobenzofurans said to be usefulas pesticides or chemical intermediates. DerWent abstract 88-312695/44refers to arylhydrazides of trifluoroacetic acid said to havefungicidal, bacteriocidal, acaricidal, and antiseptic activity. ChemicalAbstracts 105(17):152686c refers to various phenylhydrazines said tohave activity against insects and mites.

SUMMARY OF THE INVENTION

The instant invention relates to a compound having the structuralformula (I) or (II): ##STR2## wherein:

X is a) phenyl; lower phenylalkoxy; phenoxy; or benzyl; or b) onesubstituent from group a) and one or more substituents selected from C₁-C₄ alkoxy; halogen; lower alkyl; and lower alkylthio; or c) along withthe phenyl to which it is attached, forms a multiple fused ringheterocycle such as dibenzofuranyl;

Y is H, C₁ -C₄ alkanoyl, C₁ -C₄ haloalkanoyl, dialkoxyphosphoryl,alkylaminocarbonyl, haloalkylsulfonyl, or C₁ -C₄ alkoxy carbonyl; and

R is H, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₃ -C₆ cycloalkoxy, haloalkyl,alkoxyalkyl, arylalkoxy, alkenyl, alkylthio, alkoxycarbonyl, alkylamino,heteroaryl, arylalkyl, haloalkoxy, aryloxy, or C₃ -C₆ cycloalkyl; and

Z is O or S.

Further, when X includes a substituent having a phenyl ring (i.e., isphenyl, phenylalkoxy, phenoxy or benzyl), the phenyl ring is optionallysubstituted with one or more of halogen, nitro, lower alkyl, loweralkoxy, lower haloalkyl, or dialkylamino.

The instant invention further relates to pesticidal compositionscomprising:

a) an effective amount of a compound having the structure of formula (I)or (II) above as an active ingredient; and (b) an agriculturallyacceptable carrier.

The present invention is also directed to a method for controlling pestssuch as insects, acarids or nematodes which comprises applying aneffective amount of a compound of formula (I) or (II) or of acomposition of the present invention to a locus to be protected or ridof pests.

DETAILED DESCRIPTION OF THE INVENTION

The compounds of the present invention have the structure (I) or (II)defined above. Preferred compounds are those in which Y is hydrogen orCOCF₃.

The compounds having structure (I) may be prepared by reacting asubstituted phenylhydrazine: ##STR3## with an acylating agent: ##STR4##wherein Z is halo or ##STR5## and an equivalent of an HCl acceptor suchas pyridine in a solvent such as toluene. The product of this reactionmay be further acylated, or converted by oxidation with an oxidizingagent such as Pd/air to form compounds having structure (II).

The compositions of this invention comprise (a) a compound having astructure within that of formula (I) or (II) above, and (b) a suitablecarrier. Such suitable carriers may be solid or liquid in nature.

Suitable liquid carriers may be comprised of water, alcohols, ketones,phenols, toluene and xylenes. In such formulations, additivesconventionally employed in the art may be utilized such as, for example,one or more surface active agents and/or inert diluents, to facilitatehandling an application of tile resulting pesticide composition.

The pesticidal compositions may alternatively comprise solid carrierstaking the form of dusts, granules, wettable powders, pastes, aerosols,emulsions, emulsifiable concentrates, and water-soluble solids.

For example, the pesticidal compounds of this invention may be appliedas dusts when admixed with or absorbed onto powdered solid carriers,such as mineral silicates, e.g., mica, talc, pyrophyllite and clays,together with a surface-active dispersing agent so that a wettablepowder is obtained which then is applicable directly to the loci to betreated. Alternatively, the powdered solid carrier containing thecompound admixed therewith may be dispersed in water to form asuspension for application in such form.

Granular formulations of the compounds, suitable for application bybroadcasting, side dressing, soil incorporation or seed treatment, aresuitably prepared using a granular or pellitized form of carrier such asgranular clays, vermiculite, charcoal or corn cobs.

Alternatively, the pesticidal compounds may be applied in liquids orsprays when utilized in a liquid carrier, such as in a solutioncomprising a compatible solvent such as acetone, benzene, toluene orkerosene, or as dispersed in a suitable non-solvent medium, for example,water.

Another method of application to loci to be treated is aerosoltreatment, for which the compound may be dissolved in an aerosol carrierwhich is a liquid under pressure but which is a gas at ordinarytemperature (e.g., 20° C.) and atmospheric pressure. Aerosolformulations may also be prepared by first dissolving the compound in aless volatile solvent and then admixing the resulting solution with ahighly volatile liquid aerosol carrier.

For pesticidal treatment of plants (such term including plant parts),the compounds of the invention preferably are applied in aqueousemulsions containing a surface-active dispersing agent which may benon-ionic, cationic or anionic. Suitable surface-active agents includethose known in the art, such as those disclosed in U.S. Pat. No.2,547,724 (columns 3 and 4). The compounds of the invention may be mixedwith such surface-active dispersing agents, with or without an organicsolvent, as concentrates for the subsequent addition of water to yieldaqueous suspensions of the compounds at desired concentration levels.

In addition, the compounds may be employed with carriers whichthemselves are pesticidally active, such as insecticides, acaricides,fungicides or bactericides.

It will be understood that the amount of the pesticidally activecompound in a given formulation will depend upon the specific pest to becombatted, as well as upon the specific chemical composition andformulation of the compound being employed, the method of applying thecompound/formulation and the locus of treatment so that the pesticidallyeffective amount of the compound may vary widely. Generally, however,concentrations of the compound as the active ingredient in pesticidallyeffective formulations may range from about 0.1 to about 95 percent byweight. Spray dilutions may be as low as a few parts per million, whileat the opposite extreme, full strength concentrates of the compound maybe usefully applied by ultra low volume techniques. Concentration perunit area, where plants constitute the loci of treatment, may rangebetween about 0.01 and about 50 pounds per acre, with concentrations ofbetween about 0.1 and about 10 pounds per acre preferably being employedfor crops such as corn, tobacco, rice and the like.

To combat pests, sprays of the compounds may be applied to the pestsdirectly and/or to plants upon which they feed or nest. The pesticidallyactive formulations may also be applied to the soil or other medium inwhich the pests are present.

Harmful insects, nematodes and acarids attack a wide variety of plants,including both ornamental and agricultural plants and inflict damage byconsuming roots and/or foliage, withdrawing vital juices from theplants, secreting toxins and often by transmitting diseases. Thecompounds of the present invention may be advantageously utilized tominimize or prevent such damage. The specific methods of application, aswell as the selection and concentration of these compounds will, ofcourse, vary depending upon such circumstances as geographic area,climate, topography, plant tolerance, etc. For specific circumstances,one skilled in the art may readily determine the proper compound,concentration and method of application by routine experimentation.

The compounds of the invention are particularly useful as insecticides,nematicides and acaricides, for foliar and/or soil application.

EXAMPLES

The following Examples are intended to further illustrate the invention,and are not intended to limit the scope of the invention in any mannerwhatsoever.

EXAMPLE 1

Preparation of (4-methoxy-[1,1'-biphenyl]-3-yl)hydrazine hydrochloride(chemical intermediate)

To 25 g of 5-phenyl-o-anisidine were added 250 ml of water and 450 ml ofconcentrated hydrochloric acid and the stirred solution was cooled to 0°C. A solution of 8.6 g of sodium nitrite in 20 ml of water was thenadded dropwise, maintaining a temperature of 0° C. After this additionthe mixture was stirred, at 0° C. for 1 hour. A solution of 113 g ofstannous chloride in 200 ml of concentrated HCl, cooled to -20° C., wasadded to the reaction mixture and again the mixture was stirred for onehour. The mixture was then suction filtered and the resulting solid wasallowed to dry overnight. The solid was dissolved in hot water, gravityfiltered, and the filtrate cooled on ice. The crystallized solid wasthen suction filtered and the product was allowed to dry overnight. Theproduct obtained was 26 g of (4-methoxy-[1,1'-biphenyl]-3-yl)hydrazinehydrochloride.

EXAMPLE 2

Preparation of 2-(4-methoxy-[1,2'-biphenyl]-3-yl)hydrazide of propanoicacid (Compound 18)

To 5 g of the product of Example 1 was added 100 ml of water and 40 mlof 10% sodium hydroxide solution and the mixture was allowed to stir for1 hour at room temperature. The mixture was then extracted with etherand the ether extract was dried over sodium sulfate for one half hour.The ether extract was then filtered and evaporated under reducedpressure to yield 4.6 g of the intermediate,(4-methoxy-[1,1'-biphenyl]-3-yl)hydrazine.

To 4.6 g of the above intermediate, 150 ml of toluene and 1.58 g ofpyridine were added and the solution was stirred and cooled to 0° C.Then, 1.84 g of propionyl chloride was added dropwise. After addition ofthe propionyl chloride, the solution was stirred for 1 hour at 0° C. Thesolution was then washed twice, each time with 100 ml of water. Thewater fraction was saved and extracted with toluene. The toluenefractions from the extraction were combined and evaporated under reducedpressure. The resulting solid was washed with hexane and filtered. Theproduct obtained was 3.4 g of2-(4-methoxy-[1,1'-biphenyl]-3-yl)hydrazide of propanoic acid.

EXAMPLE 3

Preparation of2-(4-methoxy-[1,1'-biphenyl]-3-yl)-2-(trifluoroacetyl)hydrazide ofpropanoic acid (Compound 73)

To 2.25 g of the product of Example 2 was added 150 ml of methylenechloride. The solution was stirred and cooled to 0° C. Then 1.75 g oftrifluoroacetic anhydride was added dropwise, the flask stoppered, andthe reaction stirred overnight. The solvent was then evaporated underreduced pressure to yield a solid which was washed with hexane andfiltered. The final product obtained was 2.7 g of2-(4-methoxy-[1.1'-biphenyl]-3-yl)-2-(trifluoroacetyl)hydrazide ofpropanoic acid, with a melting point of 126° C.

EXAMPLE 4

Preparation of (4-bromo-[1,1'-biphenyl]-3-yl)hydrazine hydrochloride(chemical intermediate)

To 4 g of 4-bromo-[1,1'-biphenyl]-3-amine were added 25 ml of water and50 ml of concentrated HCl with stirring. The solution was cooled to 0°C. A solution of 1.1 g of sodium nitrite in 6 ml of water was then addeddropwise while maintaining a temperature of 0° C. After this addition,the mixture was stirred at 0° C. for one hour. A solution of 20 g ofstannous chloride in 20 ml of concentrated HCl cooled to -20° C. wasadded to the reaction mixture and again the mixture was stirred for onehour.

The precipitate was then suction filtered and the resulting solid wasallowed to dry overnight. The product, (4-bromo-[1,1'-biphenyl]hydrazinehydrochloride, was used in subsequent reactions without furtherpurification.

EXAMPLE 5

Preparation of isopropyl 2-(4-bromo-[1,1'-biphenyl]-3-yl) hydrazinecarboxylate (Compound 139)

To the product of Example 4 was added 100 ml of a 10% aqueous sodiumhydroxide solution and the mixture was stirred for 30 minutes at 10° C.The mixture was then extracted with ether, dried over sodium sulfate for2 hours, and evaporated, leaving 3 g of(4-bromo-[1,1'-biphenyl]-3-yl)hydrazine. To 3 g of the hydrazine wereadded 100 ml of toluene and 1.5 g of pyridine and the resulting mixturewas cooled an ice bath. Twelve ml of a 1M solution of isopropylchloroformate in toluene were added dropwise. After the addition ofisopropyl chloroformate, the solution was allowed to stir overnight atroom temperature. The solution was then washed twice, each time with 100ml of water, dried over sodium sulfate for 2 hours, and evaporated underreduced pressure.

The resulting solid was washed with hexane and recrystallized fromtoluene. The product obtained was 3 g of isopropyl2-(4-bromo-[1,1'-biphenyl]-3-yl) hydrazinecarboxylate with melting point107°-108° C.

EXAMPLE 6

Preparation of isopropyl (4-bromo-[1,1'-biphenyl]-3-yl)diazenecarboxylate (Compound 161)

To 1.7 g of the product of Example 4 was added 100 ml of toluene and 0.4g of palladium on charcoal. The mixture was stirred overnight at roomtemperature, then filtered out and the toluene evaporated under reducedpressure. The product obtained was 1.5 g of isopropyl(4-bromo-[1,1'-biphenyl]-3-yl)diazene carboxylate as a red oil.

EXAMPLE 7

Preparation of 2-methoxy-3-dibenzofuranyl hydrazine (chemicalintermediate)

To 10 g of 3-amino-2-methoxydibenzofuran were added 100 ml of water and50 ml of concentrated HCl with stirring. The solution was cooled to 0°C. A solution of 3.5 g of sodium nitrite in 15 ml of water was thenadded dropwise, maintaining a temperature of 0° C. After this addition,the mixture was stirred at 0° C. for one hour. A solution of 40 g ofstannous chloride in 50 ml of concentrated HCl cooled to -20° C. wasadded to the reaction mixture and the mixture was stirred for one hour.

The precipitate was then suction filtered and the resulting solid addedto a solution of 70 g sodium hydroxide in 500 ml of water cooled in anice bath. The mixture was then extracted with ether, dried over sodiumsulfate for 2 hours, and evaporated to a solid. The solid was washedwith hexane, leaving 7 g of 2-methoxy-3-dibenzofuranyl hydrazine of mp113°-115° C.

EXAMPLE 8

Preparation of isopropyl 2-(2-methoxy-3-dibenzofuranyl)hydrazinecarboxylate (Compound 141)

To 2.3 g of the product of Example 7 were added 100 ml of toluene and 1g of pyridine and the resulting mixture was cooled in an ice bath. Tenml of a 1M solution of isopropyl chloroformate in toluene was then addeddropwise. After this addition, the solution was allowed to stirovernight at room temperature.

The solution was then washed twice, each time with 100 ml of water,dried over sodium sulfate for two hours, and then evaporated underreduced pressure. The resulting solid was washed with hexane andrecrystallized from toluene. The product obtained was 2 g of isopropyl2-(2-methoxy-3-dibenzofuranyl) hydrazine carboxylate with mp of 178° C.

EXAMPLE 9

Preparation of isopropyl (2-methoxy-3-dibenzofuranyl) diazenecarboxylate(Compound 157)

To 1.4 g of the product of Example 7 were added 100 ml of toluene and0.3 g of palladium on charcoal. The mixture was stirred overnight atroom temperature, filtered, and the toluene evaporated under reducedpressure. The product obtained was 1.2 g of isopropyl(2-methoxy-3-dibenzofuranyl) diazenecarboxylate as a red oil.

The compounds summarized in Tables 1-4B and numbered from 1-161 wereprepared using essentially the same processes as shown in the foregoingexamples. Where starting compounds were not commercially available, theywere synthesized by methods well known in the art. Each of the compoundsso formed is characterized by their NMR characteristics.

                                      TABLE 1                                     __________________________________________________________________________     ##STR6##                                                                     COMPOUND                                                                              X        R        Z NMR DATA FOR NOTES 1 (CDCL,.sub.3)                __________________________________________________________________________    1       2-C.sub.6 H.sub.5                                                                      CH.sub.3 O s(3)1.9; m(10)6.8-7.5; bs(1)9.9                   2       2-C.sub.6 H.sub.5                                                                      OCH.sub.3                                                                              O s(3)3.6; s(1)6.5; m(9)6.8-7.5; bs(1)9.1           3       2-C.sub.6 H.sub.5                                                                      OCH.sub.2 CH.sub.3                                                                     O t(3)1.2; q(2)4.0; s(1)6.5;                                                    m(9)6.7-7.5; bs(1)9.0                             4       2-C.sub.6 H.sub.5                                                                      C(CH.sub.3).sub.3                                                                      O s(9)1.2; m(10)6.8-7.5; bs(1)9.7                   5       2-C.sub.6 H.sub.5                                                                      C.sub.5 H.sub.9 -c                                                                     O m(8)1.4-1.8; m(1)2.4-2.8; d(1)6.5;                                            m(9)6.7-7.5; d(1)9.8                              6       2-C.sub.6 H.sub.5                                                                      OCH.sub.2 C.sub.6 H.sub.5                                                              O s(2)5.1; s(1)6.5; m(14)6.8-7.5; s(1)9.8           7       2-C.sub.6 H.sub.5                                                                      OCH(CH.sub.3).sub.2                                                                    O d(6)1.2; m(1)4.9; bs(1)5.9; bs(1)6.3;                                         m(9)6.8-7.5                                       8       3-C.sub.6 H.sub.5                                                                      CH.sub.3 O s(3)2.0; m(9)6.8-7.5; bs(1)8.7; bs(1)9.7          9       2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 Cl                                                                            O s(3)3.8; s(2)3.9; m(9)6.9-7.6; bs(1)9.8           10      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.3                                                                              O s(3)3.7; s(3)3.8; bs(1)6.2; m(9)6.7-7.5           11      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CH.sub.3                                                                     O t(3)1.2; s(3)3.8; q(2)4.2; bs(1)6.3;                                          bs(1)6.4; m(8)6.7-7.5                             12      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 CH.sub.2 CH.sub.3                                                             O t(3)0.9; m(2)1.5; t(2)2.2; s(3)3.8;                                           m(9)6.8-7.5; d(1)9.8                              13      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH(CH.sub.3).sub.2                                                                     O d(6)0.9; m(1)2.9; s(3)3.8; m(9)6.8-7.5                                        bs(1)9.8                                          14      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        C(CH.sub.3).sub.3                                                                      O s(9)1.1; s(3)3.8; m(9)6.8-7.5; bs(1)9.8           15      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 C.sub.6 H.sub.5                                                              O s(3)3.9; s(2)5.0; m(2)6.4; m(8)6.9-7.6            16      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 OCH.sub.3                                                                     O s(3)3.3; s(3)3.8; s(2)4.0; bs(1)6.5;                                          m(8)6.7-7.5; bs(1)8.3                             17      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        C(CH.sub.3)CH.sub.2                                                                    O s(3)2.0; s(3)3.8; s(1)5.2; s(1)5.7;                                           bs(1)6.5; m(8)6.7-7.5; bs(1)8.3                   18      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 CH.sub.3                                                                      O t(3)1.2; q(2)2.3; s(3)3.8; bs(1)6.5;                                          m(8)6.8-7.5; bs(1)8.3                             19      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        O(CH.sub.2).sub.3 CH.sub.3                                                             O t(3)0.9; m(4)1.5; s(3)3.8; t(2)4.1;                                           bs(1)6.5; m(8)6.8-7.5                             20      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CH.sub.2 CH.sub.3                                                            O t(3)0.9; m(2)1.6; s(3)3.8; t(2)4.1;                                           bs(1)6.3; bs(1)6.5; m(8)6.8-7.5                   21      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CH(CH.sub.3).sub.2                                                           O d(6)0.9; m(1)1.9; s(3)3.8; d(2)3.9;                                           bs(1)6.3; bs(1)6.6; m(8)6.8-7.5                   22      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        NHC.sub.3 H.sub.7                                                                      S t(3)1.0; m(2)1.7; q(2)3.6; s(3)3.9;                                           s(1)6.5; m(9)6.8-7.5; s(1)8.5                     23      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CO.sub.2 CH.sub.2 CH.sub.3                                                             O t(3)1.2; s(3)3.8; q(2)4.2; m(8)6.8-7.5;                                       bs(1)8.3; bs(1)9.8                                24      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        SCH.sub.2 CH.sub.3                                                                     O t(3)1.2; q(2)2.7; s(3)3.8; m(9)6.8-7.5;                                       bs(1)9.5                                          25      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CHCH.sub.2                                                                   O s(3)3.8; d(2)4.6; m(3)5.1-6.0; bs(1)6.3;                                      bs(1)6.5; m(8)6.8-7.5                             26      2-CH.sub.3 O, 5-C.sub. 6 H.sub.5                                                       OCH(CH.sub.3).sub.2                                                                    O d(6)1.2; s(3)3.8; m(1)5.0; bs(1)6.3;                                          bs(1)6.5; m(8)6.8-7.5                             27      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 C(CH.sub.3).sub.3                                                             O s(9)1.0; s(2)2.1; s(3)3.8; bs(1)6.5;                                          m(8)6.8-7.5                                       28      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CF.sub.2 CF.sub.3                                                                      O s(3)3.8; m(8)6.8-7.5; bs(2)8.2                    29      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CF.sub.2 Cl                                                                            O s(3)3.8; bs(1)6.0; m(8)6.8-7.5; bs(1)8.2          30      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        2-C.sub.4 H.sub.3 S                                                                    O s(3)3.8; m(13)6.7-7.9                             31      2-C.sub.6 H.sub.5                                                                      H        O m(10)6.7-7.5; bs(1)8.1; bs(1)9.9;                 32      2-C.sub.6 H.sub.5                                                                      CF.sub.3 O m(11)6.7-7.5                                      33      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        H        O s(3)3.9; m(9)6.9-7.7; bs(1)8.1; bs(1)9.8          34      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.3 O s(3)2.0; s(3)3.8; m(10)6.8-7.7                    35      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CF.sub.3 O s(3)3.8; m(10)6.8-7.7                             36      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CHClCH.sub.3                                                                           O d(3)1.5; s(3)3.9; q(1)                            37      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 C.sub.6 H.sub.5                                                               O s(2)3.5; s(3)3.9; m(15)5.8- 7.4                   38      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        cyclohexyl                                                                             O m(11)1.1-1.8; s(3)3.8;                                                        m(9)6.8-7.5; bs(1)9.8                             39      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CH.sub.2 OCH.sub.3                                                           O s(3)3.3; t(2)3.5; s(3)3.8; t(2)4.2;                                           bs(1)6.3; m(9)6.8-7.5                             40      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCHClCH.sub.3                                                                          O d(3)1.8; s(3)3.8; m(1)6.5; m(10)6.8-7.6           41      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OC.sub.6 H.sub.5                                                                       O s(3)3.8; m(15)6.5-7.8                             42      2-C.sub.6 H.sub.5                                                                      OC.sub.3 H.sub.7                                                                       O m(5)0.8-1.7; m(2)4.1; bs(1)5.9                                                m(10)6.7-7.5                                      43      2-C.sub.6 H.sub.5                                                                      OCH.sub.4 H.sub.9                                                                      O m(7)0.8-1.7; m(2)4.1; bs(1)5.9                                                m(10)6.7-7.6                                      44      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCHCH.sub.2                                                                            O s(3)3.8; m(2)4.5-5.0                                                          bs(1)6.2; m(10)6.7-7.6                            45      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OC(CH.sub.3).sub.2 CCl.sub.3                                                           O s(6)1.9; s(3)3.9; bs(1)6.2; m(9)6.8-7.6           46      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        O-cyclohexyl-                                                                          O m(8)1.0-2.2; s(3)3.9; m(10)6.5-7.5                                 3-Cl                                                         47      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CH.sub.2 Cl                                                                  O m(2)3.6; s(3)3.8; m(2)4.3; bs(1)6.2                                           m(9)6.7-7.6                                       48      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CCl.sub.3                                                                              O s(3)3.9; m(10)6.8-7.8                             49      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CHCH.sub.2                                                                   O d(2)4.5; m(3)5.0-6.0; m(11)6.7-7.6                50      3-C.sub.6 H.sub.5                                                                      OCH(CH.sub.3).sub.2                                                                    O d(6)1.2; m(1)4.9; bs(1)6.0; m(10)6.7-7.5          51      3-C.sub.6 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                       O t(3)1.2; q(2)4.1; bs(1)5.9; m(10)6.7-7.6          52      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH(CH.sub.3).sub.2                                                                    O m(9)1.2-1.6; m(2)4.0-4.3; m(1)4.8-5.2;                                        bs(1)6.4; m(9)6.8-7.6                             53      2-C.sub.6 H.sub.5                                                                      OC.sub.5 H.sub.11                                                                      O m(9)0.8-1.7; m(2)3.9-4.2; bs(1)5.9                                            m(10)6.7-7.5                                      54      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OC.sub.5 H.sub.11                                                                      O m(9)0.8-1.7; s(3)3.8; t(2)4.1; bs(1)6.3;                                      m(9)6.7-7.5                                       55      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OC.sub.6 H.sub.13                                                                      O m(11)0.8-1.7; s(3)3.9; t(2)4.1; bs(1)6.3;                                     m(9)6.7-7.5                                       136     3-OCH.sub.2 C.sub.6 H.sub.5                                                            C.sub.2 H.sub.5                                                                        O t(3)1.2; q(2)4.1; s(2)5.0; bs(2)6.3;                                          m(9)6.9-7.4                                       137     3-OCH.sub.2 C.sub.6 H.sub.5                                                            CH(CH.sub.3).sub.2                                                                     O d(6)1.3; m(1)5.0; s(2)5.1; bs(2)6.5;                                          m(9)6.9-7.5                                       138     3-OC.sub.6 H.sub.5                                                                     CH(CH.sub.3).sub.2                                                                     O s(9)1.4; bs(2)6.5; m(9)6.9-7.5                    139     2-Br, 5-C.sub.6 H.sub.5                                                                CH(CH.sub.3).sub.2                                                                     O d(6)1.3; m(1)5.0; bs(1)6.3; m(8)6.9-7.5           140     3-OC.sub.6 H.sub.5                                                                     CH(CH.sub.3).sub.2                                                                     O d(6)1.3; m(1)5.0; bs(2)6.6; m(9)6.9-7.5           143     3-OCH.sub.2 C.sub.6 H.sub.5                                                            CH.sub.3 O s(3)3.8; s(2)5.0; bs(2)6.5; m(9)7.0-7.5           144     3-OCH.sub.2 C.sub.6 H.sub.5                                                            CH.sub.2 CHCH.sub.2                                                                    O d(2)4.5; m(3)5.1-6.0; bs(2)6.5;                                               m(9)6.9-7.5                                       145     2-CH.sub.2 C.sub.6 H.sub.5                                                             C.sub.3 H.sub.7                                                                        O t(3)0.8; m(2)1.5; s(2)3.8; m(2)3.9;                                           bs(2)6.4; m(9)6.9-7.3                             146     2-CH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 CHCH.sub.2                                                                    O s(2)3.9; d(2)4.5; m(3)5.0-5.8; bs(2)6.6;                                      m(9)6.8-7.3                                       147     3-OCH.sub.2 C.sub.6 H.sub.5                                                            C(CH.sub.3).sub.3                                                                      O s(9)1.4; s(2)5.0; bs(2)6.5; m(9)6.9-7.4           148     2-CH.sub.2 C.sub.6 H.sub.5                                                             C(CH.sub.3).sub.3                                                                      O s(9)1.4; s(2)3.9; bs(2)6.2; m(9)6.9-7.3           149     3-OC.sub.6 H.sub.5                                                                     CH(CH.sub.3)C.sub.2 H.sub.5                                                            O t(3)0.8; d(3)1.2; m(2)1.5; m(1)4.8;                                           bs(2)6.5; m(9)6.9-7.4                             150     2-SCH.sub.3, 5-C.sub.6 H.sub.5                                                         CH(CH.sub.3).sub.2                                                                     O d(6)1.2; s(3)2.4; m(1)4.9; bs(2)6.6;                                          m(8)7.0-7.5                                       154     2-CH.sub.3, 5-C.sub.6 H.sub.5                                                          CH(CH.sub.3).sub.2                                                                     O d(6)1.2; s(3)2.2; m(1)4.9; bs(1)5.8;                                          bs(1)6.6; m(8)7.0-7.6                             155     2-OCH.sub.3, 5-OC.sub.6 H.sub.5                                                        CH(CH.sub.3).sub.2                                                                     O d(6)1.3; s(3)3.8; m(1)4.9; m(10)6.5-7.4           __________________________________________________________________________     NOTES FOR TABLES 1-4B                                                         (1) S = Singlet, d = doublet, t = triplet q = quartet, m = multiplet bs -     broad singlet                                                                 (2) the number in parenthesis represents the number of protons                (3) CD CL.sub.3 is deuterated chloroform                                 

                                      TABLE 2                                     __________________________________________________________________________     ##STR7##                                                                     COMPOUND                                                                              X        R         NMR DATA FOR TABLE 2 (CDCL,.sub.3)                 __________________________________________________________________________    56      2-C.sub.6 H.sub.5                                                                      H         bs(1)5.8; m(9)6.8-7.5; bs(1)8.1                    57      2-C.sub.6 H.sub.5                                                                      CH.sub.3  s(3)2.5; bs(1)6.0; m(9)6.8-7.5                     58      2-C.sub.6 H.sub.5                                                                      OCH.sub.3 s(3)3.7; bs(1)5.7; m(9)7.3-7.6                     59      2-C.sub.6 H.sub.5                                                                      OCH.sub.2 CH.sub.3                                                                      t(3)1.2; q(2)4.2; m(9)7.3-7.7; bs(1)9.7            60      2-C.sub.6 H.sub.5                                                                      C(CH.sub.3).sub.3                                                                       s(9)1.2; m(10)6.8-7.6                              61      2-C.sub.6 H.sub.5                                                                      C.sub.5 H.sub.9C                                                                        m(8)1.7; m(10)6.8-7.6                              62      2-C.sub.6 H.sub.5                                                                      OCH.sub.2 O.sub.6 H.sub.5                                                               s(2)5.2; bs(1)6.9; m(9)7.3-7.6                     63      2-C.sub.6 H.sub.5                                                                      CH.sub.3  s(3)2.0; m(9)7.3-7.9; bs(1)8.5                     64      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        H         s(3)3.9; b(1)5.5; m(8)7.0-7.7; bs(1)8.3            65      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.3  s(3)2.0; s(3)3.8; bs(1)6.1; m(8)6.9-7.7            66      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.3 s(3)3.7; s(3)3.9; bs(1)4.2; m(8)7.3-7.8            67      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CH.sub.3                                                                      t(3)1.1; s(3)3.8, q(2)4.1; m(9)7.2-7.8             68      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        N(CH.sub.3).sub.2                                                                       s(6)3.0; s(3)3.9; m(9)7.0-7.9                      69      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 CH.sub.2 CH.sub.3                                                              t(3)1.0; m(2)1.7; t(2)3.0; s(3)3.9;                                           m(8)7.0-7.7; bs(1)8.2                              70      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH(CH.sub.3).sub.2                                                                      d(6)1.0; m(1)2.5; s(3)3.9; bs(1)5.4;                                          m(8)7.0-7.9                                        71      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        C(CH.sub.3).sub.3                                                                       s(9)1.2; s(3)3.9; m(8)7.0-7.9; bs(1)8.3            72      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 C.sub.6 H.sub.5                                                               s(3)3.8; s(2)5.1; m(8)7.1-7.8; bs(1)9.5            73      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 CH.sub.3                                                                       t(3)1.1; q(2); s(3)3.8;                                                       m(8)7.0-7.8; bs(1)8.1                              74      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                    m(7)0.8-1.7; s(3)3.9; t(2)4.1;                                                m(9)7.0-7.8                                        75      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        C(CH.sub.3)CH.sub.2                                                                     s(3)2.0; s(3)3.9; m(2)5.4- 5.7;                                               m(8)7.0-7.8; bs(1)8.3                              76      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CF.sub.3  s(3)3.9; m(9)7.1-7.8                               77      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        N(CH.sub.2 CH.sub.3).sub.2                                                              t(6)1.2; m(4)3.3; s(3)3.8; m(9)7.0-8.0             79      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        SCH.sub.2 CH.sub.3                                                                      t(3)1.2; q(2)2.8; s(3)3.9; m(9)7.2-7.8             78      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CO.sub.2 CH.sub.2 CH.sub.3                                                              t(3)1.3; s(3)3.8; q(2)4.2; m(8)7.0-7.9;                                       bs(1)9.5                                           80      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CHCH.sub.2                                                                    s(3)3.9; d(2)4.6; m(3)5.1-5.8;                                                m(9)7.0-7.7                                        81      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH(CH.sub.3).sub.2                                                                     d(6)1.2; s(3)3.8; m(1)4.9; m(9)7.0-7.7             82      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 C(CH.sub.3).sub.3                                                              s(9)1.0; s(2)2.2; s(3)3.9; m(8)7.0-7.8;                                       bs(1)8.6                                           83      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CF.sub.2 Cl                                                                             s(3)3.9; m(9)7.0-8.0                               84      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        2-C.sub.4 H.sub.3 S                                                                     s(3)3.9; m(12)7.0-8.0                              85      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        2-C.sub.4 H.sub.3 O                                                                     s(3)3.9; bs(1)6.5; m(11)7.0-8.0                    86      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CH.sub.3                                                                      m(6)1.3; m(4)4.2; m(9)7.0-7.8                      87      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 Cl                                                                             s(3)3.9; s(2)4.0; m(9)6.9-7.7                      88      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 C.sub.6 H.sub.5                                                                s(2)3.7; s(3)3.8; m(14)6.8-7.9                     89      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        cyclohexyl                                                                              m(11)1.1-1.9; s(3)3.9; m(9)6.8-7.9                 90      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OC.sub.3 H.sub.7                                                                        t(3)1.9; m(2)1.6; s(3)3.9; t(2)4.1;                                           m(9)6.9-7.8                                        91      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.2 OCH.sub.3                                                                      s(3)3.4; s(3)3.9; s(2)4.0; m(9)6.9-7.9             92      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CH(CH.sub.3).sub.2                                                            d(6)0.9; m(1)1.8; s(3)3.9; d(2)4.0;                                           m(9)6.9-7.8                                        93      2-C.sub.6 H.sub.5                                                                      OCH.sub.2 CH(CH.sub.3)                                                                  d(6)0.9; m(1)1.8; d(2)3.9; bs(1)6.1;                                          m(9)7.2-7.7                                        94      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        CH.sub.3  t(3)1.5; s(3)2.0; s(3)4.1; m(8)6.9-7.8;                                       bs(1)8.3                                           95      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH(CH.sub.3).sub.2                                                                     d(6)1.3; m(1)5.0; m(9)7.3-7.8; bs(1)10.7           96      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH.sub.2 CH.sub.2 Cl                                                                   t(2)3.7; s(3)3.9; t(2)4.3; m(9)6.9-7.8             97      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OC.sub.6 H.sub.5                                                                        s(3)3.9; m(14)6.8-7.9                              98      2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OC.sub.4 H.sub.9                                                                        m(7)0.8-1.7; m(2)4.1; bs(1)6.2                                                m(9)7.2-7.6                                        99      2-C.sub.6 H.sub.5                                                                      OC.sub.3 H.sub.7                                                                        m(5)0.8-1.6; m(2)4.0; bs(1)6.2;                                               m(9)7.0-7.7                                        100     2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCHCH.sub.2                                                                             s(3)3.9; m(2)4.5-5.0; s(1)6.2;                                                m(10)6.8-7.8                                       101     2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OC.sub.5 H.sub.11                                                                       m(9)0.8-1.6; s(3)3.8; m(2)4.1-6.2;                                            m(9)6.8-7.7                                        102     2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OC.sub.6 H.sub.13                                                                       m(11)0.8-1.6; s(3)3.8; m(2)4.1; m(9)                                          6.8-7.7                                            __________________________________________________________________________     NOTES FOR TABLES 1-4B                                                         (1) S = Singlet, d = doublet, t = triplet q = quartet, m = multiplet bs -     broad singlet                                                                 (2) the number in parenthesis represents the number of protons                (3) CD CL.sub.3 is deuterated chloroform                                 

                                      TABLE 3                                     __________________________________________________________________________     ##STR8##                                                                     COMPOUND                                                                              Y       R      NMR DATA FOR TABLE 3 (CDCL,.sub.3)                     __________________________________________________________________________    103     COCH.sub.3                                                                            CF.sub.3                                                                             s(3)2.0; s(3)3.9; m(9)7.2-7.8                          104     COCH.sub.2 Cl                                                                         CH.sub.3                                                                             5(3)2.3; s(3)3.9; s(2)4.5; m(9)7.2-7.8                 105     COCF.sub.2 CF.sub.3                                                                   CH.sub.3                                                                             s(3)2.5; s(3)3.9; m(9)7.0-7.6                          106     COCF.sub.2 CF.sub.3                                                                   OCH.sub.3                                                                            s(3)3.4; s(3)3.9; s(2)4.0; m(8)7.0-8.0;                                       bs(1)8.8                                               107     COCH.sub.2 CH.sub.3                                                                   CF.sub.3                                                                             t(3)1.0; m(2)2.2; s(3)3.9; m(8)7.0-7.9;                                       bs(1)9.0                                               108     CO.sub.2 CH.sub.2 CH.sub.3                                                            CF.sub.3                                                                             t(3)1.2; s(3)3.9; q(2)4.2; m(9)7.0-7.8                 109     CONHCH.sub.3                                                                          OCH.sub.2 CH.sub.3                                                                   t(3)1.2; d(3)2.9; s(3)3.9; m(10)7.0-7.8                110     COCH.sub.3                                                                            CH.sub.3                                                                             s(3)2.0; s(3)3.4; s(3)3.9; m(8)6.9-7.7;                                       bs(1)9.8                                               111     COCF.sub.2 Cl                                                                         CH.sub.3                                                                             s(3)2.0; s(3)3.9; m(9)6.7-7.8                          112     COCH.sub.3                                                                            CF.sub.2 CF.sub.3                                                                    s(3)2.0; s(3)3.9; m(8)6.9-7.8; bs(1)8.9                113     COCH.sub. 3                                                                           CF.sub.2 Cl                                                                          s(3)2.0; s(3)3.9; m(8)6.9-7.8; bs(1)8.7                114     COCF.sub.2 CF.sub.3                                                                   CF.sub.3                                                                             s(3)3.9; m(9)6.9-7.9                                   115     COCF.sub.2 Cl                                                                         CF.sub.3                                                                             s(3)3.9; m(9)6.9-7.8                                   116     PO(OC.sub.2 H.sub.5).sub.2                                                            CF.sub.3                                                                             t(6)1.3; s(3)3.8; q(4)4.2; m(9)6.8-7.5                 117     COCH.sub.2 Cl                                                                         CF.sub.3                                                                             s(3)3.9; s(2)4.1; m(9)6.8-7.8                          118     COCF.sub.2 CF.sub.3                                                                   OCH(CH.sub.3).sub.2                                                                  d(6)1.2; s(3)3.9; m(1)4.9; m(9)6.9-7.8                 119     COCF.sub.2 Cl                                                                         OCH(CH.sub.3).sub.2                                                                  d(6)1.2; s(3)3.8; m(1)4.9; m(9)6.9-7.8                 120     CONHCH.sub.3                                                                          OCH(CH.sub.3).sub.2                                                                  d(6)1.2; d(3)2.8; s(3)3.8; m(1)4.9;                                           m(1)5.3; m(9)6.9-7.8                                   121     COCCl.sub.3                                                                           CF.sub.3                                                                             s(3)3.9; m(9)6.8-7.7                                   122     CON(CH.sub.3).sub.2                                                                   OCH(CH.sub.3).sub.2                                                                  d(6)1.4; s(6)2.7; s(3)3.9; m(1)5.0;                                           m(9)6.8-7.8                                            123     COCF.sub.2 CF.sub.3                                                                   CF.sub.2 Cl                                                                          d(3)3.8; m(8)6.8-7.8; bs(1)8.5                         124     COCF.sub.2 CF.sub.3                                                                   CF.sub.3                                                                             d(3)3.8; m(8)6.8-7.7; bs(1)8.6                         125     SO.sub.2 CF.sub.3                                                                     CF.sub.3                                                                             d(3)3.8; m(9)6.8-7.8                                   126     CO.sub.2 CH.sub.3                                                                     CF.sub.3                                                                             s(3)3.8; s(3)3.9; m(9)6.8-7.8                          127     COCF.sub.2 CF.sub.3                                                                   OCH.sub.2 C.sub.6 H.sub.5                                                            s(3)3.8; s(2)5.0; m(14)6.8-7.8                         128     CONHCH.sub.3                                                                          CF.sub.3                                                                             bs(3)2.7; s(3)3.8; bs(1)5.5;                                                  m(8)6.8-7.8; s(1)9.2                                   129     COCH.sub.3                                                                            OCH.sub.3                                                                            s(3)3.7; s(3)3.8; m(9)6.8-7.8                          130     CONHC.sub.2 H.sub.5                                                                   CF.sub.3                                                                             t(3)1.1; m(2)3.1; s(3)3.8; bs(1)5.8;                                          m(9)6.8-7.8                                            131     CONHC.sub.2 H.sub.5                                                                   OCH(CH.sub.3).sub.2                                                                  m(9)1.2; m(2)3.2; s(3)3.8; m(1)4.9;                                           m(9)6.8-7.8                                            132     COCH.sub.3                                                                            OCHCH.sub.2                                                                          s(3)2.0; s(3)3.8; m(2)4.4-4.9; m(1)6.5;                                       m(9)6.8-7.8                                            133     PO(OCH.sub.2 H.sub.5).sub.2                                                           OCH(CH.sub.3).sub.2                                                                  m(12)1.3; s(3)3.9; m(4)4.1; m(1)5.0;                                          m(9)6.8-7.7                                            134     PO(OC.sub.2 H.sub.5).sub.2                                                            OCH.sub.2 CH.sub.3                                                                   m(9)1.2; s(3)3.8; q(6)4.1; m(9)6.8-7.7                 __________________________________________________________________________     NOTES FOR TABLES 1-4B                                                         (1) S = Singlet, d = doublet, t = triplet q = quartet, m = multiplet bs -     broad singlet                                                                 (2) the number in parenthesis represents the number of protons                (3) CD CL.sub.3 is deuterated chloroform                                 

                                      TABLE 4                                     __________________________________________________________________________     ##STR9##                                                                     COMPOUND                                                                              X        R      NMR DATA FOR TABLE 4 (CDCL,.sub.3)                    __________________________________________________________________________    135     2-CH.sub.3 O, 5-C.sub.6 H.sub.5                                                        OCH(CH.sub.3).sub.2                                                                  d(6)1.5; s(3)4.0; m(1)5.2; m(8)7.0-7.9                156     3-OC.sub.6 H.sub.5                                                                     OC(CH.sub.3).sub.3                                                                   s(9)1.6; m(9)7.0-7.5                                  158     3-OCH.sub.2 C.sub.6 H.sub.5                                                            OC.sub.2 H.sub.5                                                                     t(3)1.4; q(2)4.4; s(2)5.0; m(9)7.1-7.5                159     2-CH.sub.3, 5-C.sub.6 H.sub.5                                                          OCH(CH.sub.3).sub.2                                                                  d(6)1.5; s(3)2.7; m(1)5.2; m(8)7.2-7.8                160     2-OCH.sub.3, 5-OC.sub.6 H.sub.5                                                        OCH(CH.sub.3).sub.2                                                                  d(6)1.4; s(3)4.0; m(1)5.2; m(8)6.9-7.4                161     2-Br, 5-C.sub.6 H.sub.5                                                                OCH(CH.sub.3).sub.2                                                                  d(6)1.5; m(1)5.3; m(8)7.0-7.7                         __________________________________________________________________________

                                      TABLE 4A                                    __________________________________________________________________________     ##STR10##                                                                    COMPOUND                                                                              R       NMR DATA FOR TABLE 4A (CDCL.sub.3)                            __________________________________________________________________________    141     CH(CH.sub.3).sub.2                                                                    d(6)1.2; s(3)3.9; m(1)5.0; bs(2)6.5; m(6)7.0-7.6              142     C(CH.sub.3).sub.3                                                                     s(9)1.5; s(3)4.0; bs(2)6.5; m(6)7.1-7.6                       151     CH.sub.2 CHCH.sub.2                                                                   s(3)4.0; d(2)4.7; m(3)5.1-5.8; bs(2)6.5; m(6)7.1-7.6          152     CH.sub.3                                                                              s(3)3.8; s(3)4.0; bs(2)6.5; m(6)7.0-7.6                       153     C.sub.3 H.sub.7                                                                       t(3)1.0; m(2)1.6; s(3)4.0; m(2)4.2; bs(2)6.6;                 __________________________________________________________________________                    m(6)7.1-7.6                                               

                  TABLE 4B                                                        ______________________________________                                         ##STR11##                                                                                        NMR DATA FOR TABLE                                        COMPOUND  R         4B (CDCL.sub.3)                                           ______________________________________                                        157       CH(CH.sub.3).sub.2                                                                      d(6)1.4; s(3)4.1; m(6)7.1-7.7                             ______________________________________                                    

EXAMPLE 10 Preparation of Formulations

The remaining examples relate to the pesticidal use of the compounds ofthis invention. In all these examples a stock solution for the compoundswere prepared at 3000 ppm by dissolving 0.3 gram of the compound to betested in 10 ml of acetone and adding 90 ml of distilled water plus fordrops of ethoxylated sorbitan monolaurate, or a simliar suitable wettingagent. For each example that follows, this stock solution was used andthe specified dilutions made. All the tests discussed below, whichinvolved treatment with compounds of this invention, were alwaysrepeated with controls, in which the active compound was not provided,to permit a comparison upon which the percent control was calculated.

EXAMPLE 11

Mite Adulticide and Mite Ovicide/Larvicide Tests

One day before treatment, a "figure 8" configuration of tree tanglefootwas applied to each of two cowpea primary leaves, one from each of twoplants in a pot. In each figure, the circle nearer the stem wasdesignated for the mite ovicide/larvicide test and the circle furtherfrom the stem was designated for the mite adulticide test.

Groups of adult mites (Tetranychus urticae Koch) were transferred intoovicide circles one day before treatment and the females were allowed todeposit eggs until one hour before treatment when they were removed.Plants were sprayed to run off with a 1000 ppm solution diluted from the3000 ppm stock solution.

One day following treatment, groups of approximately 25 adult mites weretransferred into the adulticide rings. Five days later these rings wereexamined for live mites remaining on the leaves. The percent control wasestimated based on the number of mites surviving on the check plants.

Nine days following treatment the ovicide/larvicide rings were examinedfor hatched eggs and living immature mites. The percent control wasestimated based on the number of eggs hatching and immature mitessurviving on the check plants. When the treatment effect was to eggs,control was designated as ovicidal (O); when the treatment effect was toimmatures, control was designated as larvicidal (L).

Results of the mite adulticide (MI) and ovicide/larvicide (MIOLV) testsare presented in Table 5.

                  TABLE 5                                                         ______________________________________                                        COMPOUND                                                                      NO.              MI     MIOVL                                                 ______________________________________                                        1                50     80(L)                                                 2                100    100                                                   3                100    100(L)                                                4                100    100(L)                                                5                30     80(L)                                                 6                100    100(L)                                                7                100    100(O)                                                8                70     0                                                     9                70     0                                                     10               100    100(O/L)                                              11               100    100(O/L)                                              12               95     90(L)                                                 13               70     70(L)                                                 14               100    100(L)                                                15               100    100(L)                                                16               100    100(L)                                                17               70     0                                                     18               98     100(L)                                                19               100    100(O)                                                20               100    100(O)                                                21               100    100(O)                                                22               100    20(L)                                                 23               70     0                                                     24               100    70(L)                                                 25               100    100(O)                                                26               100    100(O)                                                27               99     50(L)                                                 28               100    100(L)                                                29               80     80(L)                                                 30               50     50(L)                                                 39               100    100(L)                                                40               50     0                                                     41               80     50(L)                                                 42               100    100(O)                                                43               100    100(O)                                                44               50     30(L)                                                 45               70     50(L)                                                 46               100    30(L)                                                 47               100    100(L)                                                49               100    100(O)                                                50               100    100(O)                                                51               100    100(O)                                                52               100    100(O)                                                53               100    100(L)                                                54               100    100(O)                                                55               100    100(O)                                                56               70     0                                                     57               90     95(L)                                                 58               100    30                                                    59               100    0                                                     60               100    100(L)                                                62               98     50(L)                                                 63               100    70(L)                                                 64               100    100(L)                                                65               100    100(L)                                                66               70     50(L)                                                 67               90     95(L)                                                 68               100    100(L)                                                69               100    100(L)                                                70               100    100(L)                                                72               0      50(L)                                                 73               100    100(L)                                                74               99     30(L)                                                 75               100    100(L)                                                76               100    100(L)                                                77               100    100(L)                                                78               100    100(L)                                                79               70     70(L)                                                 80               100    70(L)                                                 81               99     90(L)                                                 82               95     30(L)                                                 83               100    100(L)                                                84               100    100(L)                                                85               100    100(L)                                                86               100    100(L)                                                93               100    80(1)                                                 94               100    100(L)                                                95               100    100(L)                                                96               100    100(L)                                                97               70     30(L)                                                 98               100    100(L)                                                99               100    100(L)                                                101              70     80(L)                                                 102              70     0                                                     105              95     0                                                     107              100    50(L)                                                 108              100    100(O)                                                109              100    100(O)                                                112              60     0                                                     114              100    100(O)                                                115              100    100(L)                                                116              100    100(L)                                                117              100    100(L)                                                118              100    100(L)                                                119              100    100(L)                                                120              100    100(L)                                                121              100    100(L)                                                122              100    100(O)                                                124              100    100(L)                                                125              80     30(L)                                                 126              100    100(L)                                                128              100    100(L)                                                130              100    50(L)                                                 131              100    100(L)                                                133              100    100(O)                                                135              100    100(O)                                                136              98     100(L)                                                137              100    100(L)                                                138              100    98(L)                                                 139              100    100(L)                                                140              100    100(L)                                                141              70     100(L)                                                142              50     80(L)                                                 143              70     30(O)                                                 144              30     0                                                     145              100    90(L)                                                 146              70     50(L)                                                 147              100    100(L)                                                148              70     30(L)                                                 149              30     0                                                     150              80     0                                                     151              0      0                                                     152              0      0                                                     153              100    90(L)                                                 154              100    100(L)                                                155              0      0                                                     156              98     0                                                     157              30     80(L)                                                 158              100    98(O)                                                 159              100    100(O)                                                160              100    20(O)                                                 161              100    100(O)                                                ______________________________________                                         NOTES:                                                                        MI = MITE ADULTICIDE                                                          MIOVL = MITE OVICIDE/LARVICIDE                                           

EXAMPLE 12 European Red Mite Test

Orchard apple trees with infestations of European red mite (Panonychusulmi) were sprayed with aqueous solutions of emulsifiable concentratesof individual compounds. Greater than 75 percent control with anapplication rate of 150 ppm ai was achieved by compound numbers 103, 10,11, 19, 20, 25, 26, and 82.

EXAMPLE 13 Nematode Test

The stock solution of 3000 ppm was diluted to 1000 ppm. For eachcompound, 25 ml was drenched onto 500 grams of soil infested with rootknot nematode (Meloidogyne incognita) eggs in a pot, for a soilconcentration of 50 ppm sc.

One day after treatment, two tomato seedlings were planted in each pot.Nineteen days after planting, the roots were evaluated for the presenceof knots or galls, and the percent control was estimated based on theinfestation levels in check plants.

The results of the testing of nematodes (NE) are given in Table 6.

EXAMPLE 14 Rice Planthopper Foliar Test

The stock solution of 3000 ppm was diluted to 1000 ppm. One potcontaining approximately 20 Mars variety rice seedlings was treated witheach formulation by spraying with a spray atomizer. One day aftertreatment plants were covered with a tubular cage and twenty adult ricedelphacids, Sogatodes oryzicola, were transferred into each cage. Fivedays after transferring, counts were made of the surviving planthoppersin each pot and percent control was estimated.

The results of the testing of rice planthoppers (RPH) are given in Table6.

EXAMPLE 15 Tobacco Budworm Test

The stock solution of 3000 ppm was used for this test. For eachcompound, 0.2 ml was piperted onto the surface of each of 5 diet cells,allowed to spread over the surfaces and air dried for two hours. Then asecond istar Heliothis virescens larva was introduced into each cell.After 14 days, the number of living larvae was determined for eachtreatment and percent control, corrected by Abbott's formula, wascalculated.

The results of the testing of tobacco budworms (TB) are given in Table6.

EXAMPLE 16 Southern Corn Rootworm Test

The stock solution of 3000 ppm was diluted to 100 ppm. For eachcompound, 2.5 ml was pipetted onto a filter paper (Whatman #3) at thebottom of a 100 mm petri dish. Two corn seedlings were soaked in the 100ppm solution for 1 hour and transferred to the petri dish. After 24hours, each dish was loaded with 5 second instar larvae of Diabroticaundecimpunctata. After five days, the number of live larvae were notedand the percent control, corrected by Abbott's formula (see J. EconomicEntomology, 18, 265-267 (1925)) was calculated.

The results appear in Table 6.

                  TABLE 6                                                         ______________________________________                                        COMPOUND      PERCENT CONTROL                                                 NO.           NE     RPH     TB     SCR                                       ______________________________________                                        1             0      30      100    0                                         2             30     100     79     75                                        3             0      100     58     50                                        4             70     100     100    100                                       5             0      0       100    0                                         6             0      100     100    0                                         7             0      100     100    100                                       8             50     PT      0      0                                         9             85     0       0      0                                         10            0      50      20     0                                         11            0      10      100    0                                         12            50     0       20     0                                         13            0      5       100    0                                         14            70     0       0      0                                         17            70     0       0      0                                         18            0      0       80     0                                         19            70     60      0      14                                        20            0      0       80     0                                         23            95     0       75     0                                         24            0      80      0      0                                         25            30     0       56     0                                         26            20     0       100    0                                         27            0      0       56     0                                         28            70     0       40     6                                         31            50     55      100    15                                        33            0      20      100    0                                         34            50     15      0      0                                         35            100    20      0      0                                         36            50     0       0      20                                        37            PT     25      80     17                                        38            0      0       80     0                                         42            0      100     100    100                                       43            0      100     100    80                                        45            0      0       100    0                                         47            80     50      0      20                                        48            50     25      0      0                                         49            0      80      0      0                                         50            30     100     0      100                                       51            30     100     100    0                                         53            0      100     100    0                                         54            0      95      80     0                                         55            0      70      40     0                                         57            0      35      100    37                                        58            0      25      100    0                                         59            50     20      100    75                                        60            0      40      60     --                                        62            0      0       100    0                                         64            70     25      0      21                                        65            60     0       0      0                                         67            0      10      100    0                                         74            0      0       80     0                                         78            95     0       0      14                                        80            0      0       78     0                                         81            0      50      78     0                                         83            30     50      73     16                                        84            0      50      20     6                                         87            50     0       0      0                                         88            50     0       100    0                                         89            0      0       60     33                                        90            0      0       100    0                                         91            0      70      80     0                                         92            0      0       75     0                                         95            0      25      100    100                                       96            30     0       50     20                                        99            0      80      0      100                                       100           70     60      0      0                                         102           70     0       0      0                                         103           0      0       100    0                                         103           0      0       100    0                                         105           0      0       100    0                                         106           30     55      0      0                                         108           70     0       0      0                                         110           0      30      100    0                                         111           0      0       100    20                                        112           50     0       0      0                                         113           0      0       100    6                                         115           70     50      16     0                                         116           60     0       0      60                                        117           50     0       55     33                                        119           0      40      78     0                                         121           50     40      0      0                                         125           98     25      0      0                                         127           50     50      0      0                                         128           70     30      0      0                                         129           50     25      0      0                                         130           70     15      0      16                                        131           70     25      0      16                                        132           70     50      0      0                                         133           0      55      60     0                                         134           70     60      0      0                                         135           --     55      --     --                                        136           100    30      20     0                                         137           100    25      0      100                                       138           0      90      0      0                                         139           0      98      0      40                                        140           0      0       0      0                                         141           100    0       60     0                                         142           0      0       60     0                                         143           PT     0       20     20                                        144           0      0       0      80                                        145           0      0       0      80                                        146           0      PT      0      20                                        147           0      0       0      100                                       148           0      0       0      100                                       149           50     0       0      60                                        150           0      0       36     0                                         151           0      0       60     20                                        152           0      0       60     0                                         153           50     0       37     0                                         154           0      80      58     0                                         155           --     0       75     0                                         156           0      0       0      0                                         157           100    0       40     0                                         158           --     --      --     --                                        159           0      100     58     0                                         160           --     0       0      0                                         161           --     100     100    60                                        ______________________________________                                         NOTES:                                                                        NE = NEMATODE                                                                 RPH = RICE PLANT HOPPER                                                       TB = TOBACCO BUDWORK                                                          SCR = SOUTHERN CORN ROOTWORK                                                  PT = PHYTOTOXIC  PLANT DIED, NO SCORE APPLICABLE                         

What is claimed is:
 1. A compound having the structural formula:##STR12## wherein X is a) phenyl; lower phenylalkoxy; phenoxy; orbenzyl; the phenyl ring of each substituent being optionally substitutedwith one or more of halogen, nitro, lower alkyl, lower alkoxy, lowerhaloalkyl or dialkylamino; or b) one substituent from group a) and oneor more substituents selected from C₁ -C₄ alkoxy; halogen; lower alkyl;and lower alkylthio;R is H, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₄haloalkyl, or C₃ -C₆ cycloalkyl; and Z is O.
 2. A compound in accordancewith claim 1 whereinX is phenyl or alkoxy; and R is CF₃, C₁ -C₄ alkyl;C₁ -C₄ alkoxy, or C₃ -C₆ cycloalkyl.
 3. A pesticidal compositioncomprisingA) a pesticidally effective amount of a compound in accordancewith claim 1; and B) an acceptable carrier.
 4. A process for controllingundesirable pests which comprises applying to a locus to be protected apesticidally effective amount of a compound in accordance with claim 1.